Laundry treatment compositions containing a fabric softener and a blue or violet dye

ABSTRACT

A laundry treatment composition which comprises a surfactant and from 0.0001 to 0.1 wt % of a combination of dyes which together have a visual effect on the human eye as a single dye having a peak absorption wavelength on cotton of from 540 nm to 650 nm, preferably from 570 mn to 630 mn, the combination comprising a photostable dye which is substantive to cotton.

This application is a continuation of application Ser. No. 10/561,563,Jun. 8, 2006, now U.S. Pat. No. 7,569,531, issued on Aug. 4, 2009.

TECHNICAL FIELD

The present invention relates to laundry treatment compositions whichcomprise dye which is substantive to cotton.

BACKGROUND AND PRIOR ART

Dyes have been included in laundry treatment products for many years.Perhaps the oldest use of dyes is to add a substantive coloured dye tocoloured clothes which require rejuvenation of colour for example asubstantive blue dye for rejuvenation of denim. These compositionsusually contain a relatively high concentration of substantive dye. Morerecently non-substantive dyes have also been used to colour otherwisewhite laundry detergent compositions. In the case of particulatedetergents this has been in the form of so-called speckles to add colourto an otherwise white powder, however laundry detergent powders whichare completely blue are also known. When dyes have been included inlaundry treatment products in this way it was regarded as essential thatnon-substantive dyes were used to prevent undesired staining of washedfabrics.

It is also known that a small amount of blue or violet dye impregnatedinto an otherwise ‘white’ fabric can appear to have enhanced whitenessas described in Industrial Dyes (K. Hunger ed Wiley-VCH 2003). Modernwhite fabrics are sold with some dye in their material in order toenhance the whiteness at the point of sale of the garment. This dye isoften blue or violet though other colours are used. However once thesegarments are worn and subsequently washed with a detergent compositionthe dye is rapidly removed from the fabric often due to dissolution by asurfactant solution. Dye is also lost by reaction with bleach in thewash and fading due to light. This results in a gradual loss ofwhiteness in addition to any other negative whiteness effects such assoiling. In many cases this leads to the appearance of a yellow colouron the cloth.

Accordingly, the present invention provides a laundry treatmentcomposition according to claim 1.

DETAILED DESCRIPTION OF INVENTION

Unless otherwise stated, all percentages or parts are on a weight basis.

Laundry Treatment Compositions

The present invention relates to compositions which are used to treatlaundry items such as clothes. Such compositions are preferably laundrydetergent compositions used for washing (especially particulatedetergents, liquid detergents, laundry bars, pastes, gels or tablets),laundry fabric conditioners used for softening fabrics, pre-treatmentproducts, post-treatment products, tumble dryer products, ironingproducts etc. Preferably they are laundry treatment products which areapplied in an aqueous environment.

The dyes may be incorporated into the treatment products in a widevariety of ways. For example dyes which are not sensitive to heat may beincluded in the slurry which is to be spray dried when the treatmentproduct is a particulate detergent composition. Another way ofincorporating dyes into particulate detergent products is to add them togranules which are post-added to the main detergent powder. In this casethere may be a concentration of dye in the granules which could presentthe danger of spotting and dye damage on the clothes to be treated. Thiscan be avoided if the concentration of dye in the granules is less than0.1%. For liquid products the dyes are simply added to the liquid andblended in substantially homogeneously.

Because the dyes are substantive, only a small amount is required toprovide the enhanced whiteness effect hence preferably the treatmentcomposition comprises from 0.0001 to 0.1 wt %, preferably from 0.0005 to0.05 wt % of the dye, more preferably from 0.001 to 0.01 wt %, mostpreferably from 0.002 to 0.008 wt %.

The Dyes

The photostable dyes of the present invention are unusual in that theyare substantive to cotton. It is preferred that the dye has asubstantivity to cotton in a standard test of greater than 7%,preferably from 8 to 80%, more preferably from 10 to 60%, mostpreferably from 15 to 40%, wherein the standard test is with a dyeconcentration such that the solution has an optical density ofapproximately 1 (5 cm pathlength) at the maximum absorption of the dyein the visible wavelengths (400-700 nm), a surfactant concentration of0.3 g/L and under wash conditions of a liquor to cloth ratio of 45:1,temperature of 20° C., soak times of 45 minutes, agitation time of 10minutes. Higher substantivities are preferred as this means less dyemust be added to the formulation to achieve the effect. This ispreferred for reasons of cost and also because excess levels of dye inthe formulation can lead to an unacceptable level of dye colour in thewash liquor and also in the powder.

A photostable dye is a dye which does not quickly photodegrade in thepresence of natural summer sunlight. A photostable dye in the currentcontext may be defined as a dye which, when on cotton, does not degradeby more than 10% when subjected to 1 hour of irradiation by simulatedFlorida sunlight (42 W/m² in UV and 343 W/m² in visible).

It is preferable that the dyes have a blue and/or violet shade. This canmean that the peak absorption frequency of the dyes absorbed on thecloth lies within the range of from 540 nm to 650 nm, preferably from570 nm to 630 nm. This effect can advantageously be achieved by acombination of dyes, each of which not necessarily having a peakabsorption within these preferred ranges but together produce an effecton the human eye which is equivalent to a single dye with a peakabsorption within one of the preferred ranges.

Organic dyes are described in Industrial Dyes (K. Hunger ed Wiley-VCH2003). A compilation of available dyes is the Colour Index published bySociety of Dyer and Colourists and American Association of TextileChemists and Colorists 2002 (see http://www.colour-index.org). Suitabledyes for the current application may be taken from any of thechromophore types, e.g. azo, anthraquinone, triarylmethane, methinequinophthalone, azine, oxazine thiazine. It is preferred that the dyedoes not contain a reactive group such as found in procion and remazoldyes. Due to the wider range available azo, anthraquinone andtriarylmethane dyes are preferred. Azo dyes are especially preferred.

Dyes are conventionally defined as being reactive, disperse, direct,vat, sulphur, cationic, acid or solvent dyes. For the purposes of thepresent invention, acid and/or direct dyes are preferred.

For use in products which contain predominately anionic surfactants,dyes containing acid groups are preferred. For use in products whichcontain predominantly cationic surfactants, dyes containing basic groupsare preferred. This is to prevent precipitation between the dye andsurfactant.

Suitable dyes for use in products containing predominately anionicsurfactants include those listed in the Colour Index as Direct VioletDyes (e.g. Direct Violet 1-108), Direct Blue dyes, Acid Blue and AcidViolet dyes.

Suitable dyes for use in products containing predominately cationicsurfactants include those listed in the Colour Index as Basic Blue andBasic Violet Dyes.

To avoid shade changes caused by pick or loss of a proton it ispreferred that the dye does not have a pKa or pKb at or near the pH ofthe product. Most preferably no pKa or pKb in the pH range of from 7 to11.

It is preferred that the dye has a high extinction coefficient, so thata small amount of dye gives a large amount of colour. Preferably theextinction coefficient at the maximum absorption of the dye is greaterthan 1000 mol⁻¹ L cm⁻¹, preferably greater than 10,000 mol⁻¹ L cm⁻¹,more preferably greater than 50,000 mol⁻¹ L cm⁻¹.

Suitable dyes can be obtained from any major supplier such as Clariant,Ciba Speciality Chemicals, Dystar, Avecia or Bayer.

Laundry Detergent Compositions

Detergent-active compounds (surfactants) may be chosen from soap andnon-soap anionic, cationic, nonionic, amphoteric and zwitterionicdetergent-active compounds, and mixtures thereof. Many suitabledetergent-active compounds are available and are fully described in theliterature, for example, in “Surface-Active Agents and Detergents”,Volumes I and II, by Schwartz, Perry and Berch. The preferreddetergent-active compounds that can be used are soaps and syntheticnon-soap anionic and nonionic compounds. The total amount of surfactantpresent is suitably within the range of from 5 to 60 wt %, preferablyfrom 5 to 40 wt %.

Anionic surfactants are well-known to those skilled in the art. Examplesinclude alkylbenzene sulphonates, particularly linear alkylbenzenesulphonates having an alkyl chain length of C₈-C₁₅; primary andsecondary alkylsulphates, particularly C₈-C₂₀ primary alkyl sulphates;alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates;dialkyl sulphosuccinates; and fatty acid ester sulphonates. Sodium saltsare generally preferred. Nonionic surfactants that may be used includethe primary and secondary alcohol ethoxylates, especially the C₈-C₂₀aliphatic alcohols ethoxylated with an average of from 1 to 20 moles ofethylene oxide per mole of alcohol, and more especially the C₁₀-C₁₅primary and secondary aliphatic alcohols ethoxylated with an average offrom 1 to 10 moles of ethylene oxide per mole of alcohol.Non-ethoxylated nonionic surfactants include alkanolamides,alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides(glucamide).

Cationic surfactants that may be used include quaternary ammonium saltsof the general formula R₁R₂R₃R₄N⁺X⁻ wherein the R groups are long orshort hydrocarbyl chains, typically alkyl, hydroxyalkyl or ethoxylatedalkyl groups, and X is a solubilising anion (for example, compounds inwhich R₁ is a C₈-C₂₂ alkyl group, preferably a C₈-C₁₀ or C₁₂-C₁₄ alkylgroup, R₂ is a methyl group, and R₃ and R₄, which may be the same ordifferent, are methyl or hydroxyethyl groups); and cationic esters (forexample, chorine esters).

Amphoteric and zwitterionic surfactants that may be used include alkylamine oxides, betaines and sulphobetaines. In accordance with thepresent invention, the detergent surfactant (a) most preferablycomprises an anionic sulphonate or sulphonate surfactant optionally inadmixture with one or more cosurfactants selected from ethoxylatednonionic surfactants, non-ethoxylated nonionic surfactants, ethoxylatedsulphate anionic surfactants, cationic surfactants, amine oxides,alkanolamides and combinations thereof.

Surfactants are preferably present in a total amount of from 5 to 60 wt%, more preferably from 10 to 40 wt %.

Laundry detergent compositions of the present invention preferablycontain a detergency builder, although it is conceivable thatformulations without any builder are possible.

Laundry detergent compositions of the invention suitably contain from 10to 80%, preferably from 15 to 70% by weight, of detergency builder.Preferably, the quantity of builder is in the range of from 15 to 50% byweight.

Preferably the builder is selected from zeolite, sodiumtripolyphosphate, sodium carbonate, sodium citrate, layered silicate,and combinations of these.

The zeolite used as a builder may be the commercially available zeoliteA (zeolite 4A) now widely used in laundry detergent powders.Alternatively, the zeolite may be maximum aluminium zeolite P (zeoliteMAP) as described and claimed in EP 384 070B (Unilever), andcommercially available as Doucil (Trade Mark) A24 from Ineos SilicasLtd, UK.

Zeolite MAP is defined as an alkali metal aluminosilicate of zeolite Ptype having a silicon to aluminium ratio not exceeding 1.33, preferablywithin the range of from 0.90 to 1.33, preferably within the range offrom 0.90 to 1.20. Especially preferred is zeolite MAP having a siliconto aluminium ratio not exceeding 1.07, more preferably about 1.00. Theparticle size of the zeolite is not critical. Zeolite A or zeolite MAPof any suitable particle size may be used.

Also preferred according to the present invention are phosphatebuilders, especially sodium tripolyphosphate. This may be used incombination with sodium orthophosphate, and/or sodium pyrophosphate.

Other inorganic builders that may be present additionally oralternatively include sodium carbonate, layered silicate, amorphousaluminosilicates.

Organic builders that may be present include polycarboxylate polymerssuch as polyacrylates and acrylic/maleic copolymers; polyaspartates;monomeric polycarboxylates such as citrates, gluconates,oxydisuccinates, glycerol mono-di- and trisuccinates,carboxymethyloxysuccinates, carboxy-methyloxymalonates, dipicolinates,hydroxyethyl-iminodiacetates, alkyl- and alkenylmalonates andsuccinates; and sulphonated fatty acid salts.

Organic builders may be used in minor amounts as supplements toinorganic builders such as phosphates and zeolites. Especially preferredsupplementary organic builders are citrates, suitably used in amounts offrom 5 to 30 wt %, preferably from 10 to 25 wt %; and acrylic polymers,more especially acrylic/maleic copolymers, suitably used in amounts offrom 0.5 to 15 wt %, preferably from 1 to 10 wt %. Builders, bothinorganic and organic, are preferably present in alkali metal salt,especially sodium salt, form.

As well as the surfactants and builders discussed above, thecompositions may optionally contain bleaching components and otheractive ingredients to enhance performance and properties.

These optional ingredients may include, but are not limited to, any oneor more of the following: soap, peroxyacid and persalt bleaches, bleachactivators, sequestrants, cellulose ethers and esters, otherantiredeposition agents, sodium sulphate, sodium silicate, sodiumchloride, calcium chloride, sodium bicarbonate, other inorganic salts,proteases, lipases, cellulases, amylases, other detergent enzymes,fluorescers, photobleaches, polyvinyl pyrrolidone, other dye transferinhibiting polymers, foam controllers, foam boosters, acrylic andacrylic/maleic polymers, citric acid, soil release polymers, fabricconditioning compounds, coloured speckles and perfume.

Detergent compositions according to the invention may suitably contain ableach system. The bleach system is preferably based on peroxy bleachcompounds, for example, inorganic persalts or organic peroxyacids,capable of yielding hydrogen peroxide in aqueous solution. Suitableperoxy bleach compounds include organic peroxides such as urea peroxide,and inorganic persalts such as the alkali metal perborates,percarbonates, perphosphates, persilicates and persulphates. Preferredinorganic persalts are sodium perborate monohydrate and tetrahydrate,and sodium percarbonate. Especially preferred is sodium percarbonatehaving a protective coating against destabilisation by moisture. Sodiumpercarbonate having a protective coating comprising sodium metaborateand sodium silicate is disclosed in GB 2 123 044B (Kao).

The peroxy bleach compound is suitably present in an amount of from 5 to35 wt %, preferably from 10 to 25 wt %.

The peroxy bleach compound may be used in conjunction with a bleachactivator (bleach precursor) to improve bleaching action at low washtemperatures. The bleach precursor is suitably present in an amount offrom 1 to 8 wt %, preferably from 2 to 5 wt %.

Preferred bleach precursors are peroxycarboxylic acid precursors, moreespecially peracetic acid precursors and peroxybenzoic acid precursors;and peroxycarbonic acid precursors. An especially preferred bleachprecursor suitable for use in the present invention isN,N,N′,N′-tetracetyl ethylenediamine (TAED). Also of interest areperoxybenzoic acid precursors, in particular, N,N,N-trimethylammoniumtoluoyloxy benzene sulphonate.

A bleach stabiliser (heavy metal sequestrant) may also be present.Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA)and the polyphosphonates such as Dequest (Trade Mark), EDTMP.

Although, as previously indicated, in one preferred embodiment of theinvention enzymes are preferably absent, in other embodiments detergentenzymes may be present. Suitable enzymes include the proteases,amylases, cellulases, oxidases, peroxidases and lipases usable forincorporation in detergent compositions.

In particulate detergent compositions, detergency enzymes are commonlyemployed in granular form in amounts of from about 0.1 to about 3.0 wt%. However, any suitable physical form of enzyme may be used in anyeffective amount.

Antiredeposition agents, for example cellulose esters and ethers, forexample sodium carboxymethyl cellulose, may also be present.

The compositions may also contain soil release polymers, for examplesulphonated and unsulphonated PET/POET polymers, both end-capped andnon-end-capped, and polyethylene glycol/polyvinyl alcohol graftcopolymers such as Sokolan (Trade Mark) HP22. Especially preferred soilrelease polymers are the sulphonated non-end-capped polyesters describedand claimed in WO 95 32997A (Rhodia Chimie).

Powder detergent composition of low to moderate bulk density may beprepared by spray-drying a slurry, and optionally postdosing(dry-mixing) further ingredients.

“Concentrated” or “compact” powders may be prepared by mixing andgranulating processes, for example, using a high-speed mixer/granulator,or other non-tower processes.

Tablets may be prepared by compacting powders, especially “concentrated”powders.

Fabric Conditioners

Cationic softening material is preferably a quaternary ammonium fabricsoftening material.

The quaternary ammonium fabric softening material compound has twoC12-28 alkyl or alkenyl groups connected to the nitrogen head group,preferably via at least one ester link. It is more preferred if thequaternary ammonium material has two ester links present.

Preferably, the average chain length of the alkyl or alkenyl group is atleast C₁₄, more preferably at least C₁₆. Most preferably at least halfof the chains have a length of C₁₈.

It is generally preferred if the alkyl or alkenyl chains arepredominantly linear.

The first group of cationic fabric softening compounds for use in theinvention is represented by formula (I):

wherein each R is independently selected from a C₅₋₃₅ alkyl or alkenylgroup, R¹ represents a C₁₋₄ alkyl, C₂₋₄ alkenyl or a C₁₋₄ hydroxyalkylgroup,T is

n is 0 or a number selected from 1 to 4, m is 1, 2 or 3 and denotes thenumber of moieties to which it relates that pend directly from the Natom, and X⁻ is an anionic group, such as halides or alkyl sulphates,e.g. chloride, methyl sulphate or ethyl sulphate.

Especially preferred materials within this formula are di-alkenyl estersof triethanol ammonium methyl sulphate. Commercial examples includeTetranyl AHT-1 (di-hardened oleic ester of triethanol ammonium methylsulphate 80% active), AT-1 (di-oleic ester of triethanol ammonium methylsulphate 90% active), L5/90 (palm ester of triethanol ammonium methylsulphate 90% active), all ex Kao. Other unsaturated quaternary ammoniummaterials include Rewoquat WE15 (C₁₀-C₂₀ and C₁₆-C₁₈ unsaturated fattyacid reaction products with triethanolamine dimethyl sulphatequaternised 90% active), ex Witco Corporation.

The second group of cationic fabric softening compounds for use in theinvention is represented by formula (II):

wherein each R¹ group is independently selected from C₁₋₄ alkyl,hydroxyalkyl or C₂₋₄ alkenyl groups; and wherein each R² group isindependently selected from C₈₋₂₈ alkyl or alkenyl groups; n is 0 or aninteger from 1 to 5 and T and X⁻ are as defined above.

Preferred materials of this class such as1,2bis[tallowoyloxy]-3-trimethylammonium propane chloride and1,2-bis[oleyloxy]-3-trimethylammonium propane chloride and their methodof preparation are, for example, described in U.S. Pat. No. 4,137,180(Lever Brothers), the contents of which are incorporated herein.Preferably these materials also comprise small amounts of thecorresponding monoester, as described in U.S. Pat. No. 4,137,180.

A third group of cationic fabric softening compounds for use in theinvention is represented by formula (III):

wherein each R¹ group is independently selected from C₁₋₄ alkyl, or C₂₋₄alkenyl groups; and wherein each R² group is independently selected fromC₈₋₂₈g alkyl or alkenyl groups; n is 0 or an integer from 1 to 5 and Tand X⁻ are as defined above.

A fourth group of cationic fabric softening compounds for use in theinvention is represented by formula (IV):

wherein each R¹ group is independently selected from C₁₋₄ alkyl, or C₂₋₄alkenyl groups; and wherein each R² group is independently selected fromC₈-C₂₈ alkyl or alkenyl groups; and X⁻ is as defined above.

The iodine value of the parent fatty acyl compound or acid from whichthe cationic softening material is formed is from 0 to 140, preferablyfrom 0 to 100, more preferably from 0 to 60.

It is especially preferred that the iodine value of the parent compoundis from 0 to 20, e.g. 0 to 4. Where the iodine value is 4 or less, thesoftening material provides excellent softening results and has improvedresistance to oxidation and associated odour problems upon storage.

When unsaturated hydrocarbyl chains are present, it is preferred thatthe cis:trans weight ratio of the material is 50:50 or more, morepreferably 60:40 or more, most preferably 70:30 or more, e.g. 85:15 ormore.

The iodine value of the parent fatty acid or acyl compound is measuredaccording to the method set out in respect of parent fatty acids inWO-A1-01/46513.

The softening material is preferably present in an amount of from 1 to60% by weight of the total composition, more preferably from 2 to 40%,most preferably from 3 to 30% by weight.

The composition optionally comprises a silicone. Typical silicones foruse in the compositions of the present invention are siloxanes whichhave the general formula R_(a)SiO_((4−a)/2) wherein each R is the sameor different and is selected from hydrocarbon and hydroxyl groups, ‘a’being from 0 to 3. In the bulk material, ‘a’ typically has an averagevalue of from 1.85-2.2.

The silicone can have a linear or cyclic structure. It is particularlypreferred that the silicone is cyclic as it is believed that cyclicsilicones deliver excellent faster drying characteristics to fabrics.

Preferably, the silicone is a polydi-C₁₋₆alkyl siloxane.

Particularly preferred is polydimethyl siloxane. The siloxane ispreferably end-terminated, if linear, either by a tri-C₁₋₆ alkylsilylgroup (e.g. trimethylsilyl) or a hydroxy-di-C₁₋₆ alkylsilyl group (e.g.hydroxy-dimethylsilyl) groups, or by both.

More preferably the silicone is a cyclic polydimethyl siloxane.

Suitable commercially available silicones include DC245(polydimethylcyclopentasiloxane also known as D5), DC246(polydimethylcyclohexasiloxane also known as D6), DC1184 (apre-emulsified polydimethylpentasiloxane also known as L5) and DC347 (apre-emulsified 100 cSt PDMS fluid) all ex Dow Corning.

The silicone may be received and incorporated into the compositioneither directly as an oil or pre-emulsified.

Pre-emulsification is typically required when the silicone is of a moreviscous nature.

Suitable emulsifiers include cationic emulsifiers, nonionic emulsifiersor mixtures thereof.

The reference to the viscosity of the silicone denotes either theviscosity before emulsification when the silicone is provided as anemulsion for incorporation into the fabric conditioning composition orthe viscosity of the silicone itself when provided as an oil forincorporation into the fabric conditioning composition.

The silicone preferably has a viscosity (as measured on a Brookfield RV4viscometer at 25° C. using spindle No. 4 at 100 rpm) of from 1 cSt toless than 10,000 centi-Stokes (cSt), preferably from 1 cSt to 5,000 cSt,more preferably from 2 cSt to 1,000 cSt and most preferably 2 cSt to 100cSt.

It has been found that drying time can be reduced using silicones havinga viscosity of from 1 to 500,000 cSt. However, it is most preferred thatthe viscosity is from 1 to less than 10,000 cSt.

The silicone active ingredient is preferably present at a level of from0.5 to 20%, more preferably from 1 to 12%, most preferably from 2 to 8%by weight, based on the total weight of the composition.

Optionally and advantageously, one or more un-alkoxylated fatty alcoholsare present in fabric conditioners of the present invention.

Preferred alcohols have a hydrocarbyl chain length of from 10 to 22carbon atoms, more preferably 11 to 20 carbon atoms, most preferably 15to 19 carbon atoms.

The fatty alcohol may be saturated or unsaturated, though saturatedfatty alcohols are preferred as these have been found to deliver greaterbenefits in terms of stability, especially low temperature stability.

Suitable commercially available fatty alcohols include tallow alcohol(available as Hydrenol S3, ex Sidobre Sinnova, and Laurex CS, exClariant).

The fatty alcohol content in the compositions is from 0 to 10% byweight, more preferably from 0.005 to 5% by weight, most preferably from0.01 to 3% by weight, based on the total weight of the composition.

It is particularly preferred that a fatty alcohol is present if thecomposition is concentrated, that is if more than 8% by weight of thecationic softening agent is present in the composition.

It is preferred that the compositions further comprise a nonionicsurfactant. Typically these can be included for the purpose ofstabilising the compositions.

Suitable nonionic surfactants include addition products of ethyleneoxide and/or propylene oxide with fatty alcohols, fatty acids and fattyamines.

Any of the alkoxylated materials of the particular type describedhereinafter can be used as the nonionic surfactant.

Suitable surfactants are substantially water soluble surfactant thegeneral formula:R—Y—(C₂H₄O)_(z)—C₂H₄OHwhere R is selected from the group consisting of primary, secondary andbranched chain alkyl and/or acyl hydrocarbyl groups; primary, secondaryand branched chain alkenyl hydrocarbyl groups; and primary, secondaryand branched chain alkenyl-substituted phenolic hydrocarbyl groups; thehydrocarbyl groups having a chain length of from 8 to about 25,preferably 10 to 20, e.g. 14 to 18 carbon atoms.

In the general formula for the alkoxylated nonionic surfactant, Y istypically:—O—, —C(O)O—, —C(O)N(R)— or —C(O)N(R)R—in which R has the meaning given above or can be hydrogen; and Z ispreferably from 8 to 40, more preferably from 10 to 30, most preferablyfrom 11 to 25, e.g. 12 to 22.

The level of alkoxylation, Z, denotes the average number of alkoxygroups per molecule.

Preferably the nonionic surfactant has an HLB of from about 7 to about20, more preferably from 10 to 18, e.g. 12 to 16.

Examples of nonionic surfactants follow. In the examples, the integerdefines the number of ethoxy (EO) groups in the molecule.

The deca-, undeca-, dodeca-, tetradeca-, and pentadecaethoxylates ofn-hexadecanol, and n-octadecanol having an HLB within the range recitedherein are useful viscosity/dispersibility modifiers in the context ofthis invention. Exemplary ethoxylated primary alcohols useful herein asthe viscosity/dispersibility modifiers of the compositions are C₁₈EO(10); and C₁₈ EO(11). The ethoxylates of mixed natural or syntheticalcohols in the “tallow” chain length range are also useful herein.Specific examples of such materials include tallow alcohol-EO(11),tallow alcohol-EO(18), and tallow alcohol-EO (25), coco alcohol-EO(10),coco alcohol-EO(15), coco alcohol-EO(20) and coco alcohol-EO(25).

The deca-, undeca-, dodeca-, tetradeca-, pentadeca-, octadeca-, andnonadeca-ethoxylates of 3-hexadecanol, 2-octadecanol, 4-eicosanol, and5-eicosanol having an HLB within the range recited herein are usefulviscosity and/or dispersibility modifiers in the context of thisinvention. Exemplary ethoxylated secondary alcohols useful herein as theviscosity and/or dispersibility modifiers of the compositions are: C₁₆EO(11); C₂₀ EO(11); and C₁₆ EO(14).

As in the case of the alcohol alkoxylates, the hexa- tooctadeca-ethoxylates of alkylated phenols, particularly monohydricalkylphenols, having an HLB within the range recited herein are usefulas the viscosity and/or dispersibility modifiers of the instantcompositions. The hexa- to octadeca-ethoxylates of p-tri-decylphenol,m-pentadecylphenol, and the like, are useful herein. Exemplaryethoxylated alkylphenols useful as the viscosity and/or dispersibilitymodifiers of the mixtures herein are: p-tridecylphenol EO(11) andp-pentadecylphenol EO(18).

As used herein and as generally recognized in the art, a phenylene groupin the nonionic formula is the equivalent of an alkylene groupcontaining from 2 to 4 carbon atoms. For present purposes, nonionicscontaining a phenylene group are considered to contain an equivalentnumber of carbon atoms calculated as the sum of the carbon atoms in thealkyl group plus about 3.3 carbon atoms for each phenylene group.

The alkenyl alcohols, both primary and secondary, and alkenyl phenolscorresponding to those disclosed immediately hereinabove can beethoxylated to an HLB within the range recited herein and used as theviscosity and/or dispersibility modifiers of the instant compositions.

Branched chain primary and secondary alcohols which are available fromthe well-known “OXO” process can be ethoxylated and employed as theviscosity and/or dispersibility modifiers of compositions herein.

Suitable polyol based surfactants include sucrose esters such sucrosemonooleates, alkyl polyglucosides such as stearyl monoglucosides andstearyl triglucoside and alkyl polyglycerols.

The above nonionic surfactants are useful in the present compositionsalone or in combination, and the term “nonionic surfactant” encompassesmixed nonionic surface active agents.

The nonionic surfactant is present in an amount from 0.01 to 10%, morepreferably 0.1 to 5%, most preferably 0.35 to 3.5%, e.g. 0.5 to 2% byweight, based on the total weight of the composition.

The fabric conditioner compositions of the invention preferably compriseone or more perfumes.

It is well known that perfume is provided as a mixture of variouscomponents. Suitable components for use in the perfume include thosedescribed in “Perfume and Flavor Chemicals (Aroma Chemicals) by SteffenArctander, published by the author 1969 Montclait, N.J. (US), reprinted1^(st) Apr. 1982 library of Congress Catalog Number 75-91398.

The perfume is preferably present in an amount from 0.01 to 10% byweight, more preferably 0.05 to 5% by weight, most preferably 0.5 to4.0% by weight, based on the total weight of the composition.

The liquid carrier employed in the instant compositions is at leastpartly water due to its low cost, relative availability, safety, andenvironmental compatibility. The level of water in the liquid carrier ismore than about 50%, preferably more than about 80%, more preferablymore than about 85%, by weight of the carrier. The level of liquidcarrier is greater than about 50%, preferably greater than about 65%,more preferably greater than about 70%. Mixtures of water and a lowmolecular weight, e.g. <100, organic solvent, e.g. a lower alcohol suchas ethanol, propanol, isopropanol or butanol are useful as the carrierliquid. Low molecular weight alcohols including monohydric, dihydric(glycol, etc.) trihydric (glycerol, etc.), and polyhydric (polyols)alcohols are also suitable carriers for use in the compositions of thepresent invention.

Co-active softeners for the cationic surfactant may also be incorporatedin an amount from 0.01 to 20% by weight, more preferably 0.05 to 10%,based on the total weight of the composition. Preferred co-activesofteners include fatty esters, and fatty N-oxides.

Preferred fatty esters include fatty monoesters, such as glycerolmonostearate (hereinafter referred to as “GMS”). If GMS is present, thenit is preferred that the level of GMS in the composition is from 0.01 to10% by weight, based on the total weight of the composition.

The co-active softener may also comprise an oily sugar derivative.Suitable oily sugar derivatives, their methods of manufacture and theirpreferred amounts are described in WO-A1-01/46361 on page 5 line 16 topage 11 line 20, the disclosure of which is incorporated herein.

It is useful, though not essential, if the compositions comprise one ormore polymeric viscosity control agents. Suitable polymeric viscositycontrol agents include nonionic and cationic polymers, such ashydrophobically modified cellulose ethers (e.g. Natrosol Plus, exHercules), cationically modified starches (e.g. Softgel BDA and SoftgelBD, both ex Avebe). A particularly preferred viscosity control agent isa copolymer of methacrylate and cationic acrylamide available under thetradename Flosoft 200 (ex SNF Floerger).

Nonionic and/or cationic polymers are preferably present in an amount of0.01 to 5 wt %, more preferably 0.02 to 4 wt %, based on the totalweight of the composition.

Other optional nonionic softeners, bactericides, soil-releases agentsmay also be incorporated in fabric conditioners of the invention.

The compositions may also contain one or more optional ingredientsconventionally included in fabric conditioning compositions such as pHbuffering agents, perfume carriers, fluorescers, colourants,hydrotropes, antifoaming agents, antiredeposition agents,polyelectrolytes, enzymes, optical brightening agents, pearlescers,anti-shrinking agents, anti-wrinkle agents, anti-spotting agents,antioxidants, sunscreens, anti-corrosion agents, drape imparting agents,preservatives, anti-static agents, ironing aids and other dyes.

The product may be a liquid or solid. Preferably the product is a liquidwhich, in its undiluted state at ambient temperature, comprises anaqueous liquid, preferably an aqueous dispersion of the cationicsoftening material.

When the product is an aqueous liquid, it preferably has a pH of greaterthan 1.5 and less than 5, more preferably greater than 2 and less than4.5.

The fabric conditioner composition is preferably used in the rinse cycleof a home textile laundering operation, where, it may be added directlyin an undiluted state to a washing machine, e.g. through a dispenserdrawer or, for a top-loading washing machine, directly into the drum.Alternatively, it can be diluted prior to use. The compositions may alsobe used in a domestic hand-washing laundry operation.

EXAMPLES Example 1

To determine the substantivity of a range of dyes the followingexperiment was performed. A stock solution of 1.5 g/L of a base washingpowder in water was created. The washing powder contained 18% NaLAS, 73%salts (silicate, sodium tri-poly-phosphate, sulphate, carbonate), 3%minors including perborate, fluorescer and enzymes, remainder impuritiesand water. The solution was divided into 60 ml aliquots and dye added tothis to give a solution of optical density of approximately 1 (5 cmpathlength) at the maximum absorption of the dye in the visible lengths,400-700 nm. The optical density was measured using a UV-visiblespectrometer. 1 piece of bleached, non-mercerised, non-fluorescent wovencotton cloth (ex Phoenic Calico) weighing 1.3 g was placed in thesolution at room temperature (20° C.). This cloth represents a slightlyyellow cotton. The cloth was left to soak for 45 minutes then thesolution agitated for 10 mins, rinsed and dried. Following this theoptical density of the solution was re-measured and the amount of dyeabsorbed by the cloth calculated. This experiment was repeated for eachdye and 4 replicates were done per dye.

The dyes used and the % deposition is given in table 1. Table 2 givesthe maximum extinction coefficient, ε_(max), in the wash solution andthe peak absorption wavelength in solution and on cotton. All values arereported to 2 significant figures.

TABLE 1 Dye % Deposition Acid Black 1 23 Food Black 1 0.50 Direct Blue 148 Direct Violet 51 69 Direct Blue 71 34 Acid Violet 9 2.1 Acid Blue 806.8 Acid Violet 17 18 Acid Red 88 47 Acid Red 150 33

TABLE 2 λ_(max) [nm] ε,_(ax) in solution, Dye Type [mol⁻¹L cm⁻¹] oncotton Acid Black 1 Azo 51000 620, 630 Food Black 1 Azo 41000 570, 590Direct Blue 1 Azo 120000 600, 640 Direct Violet 51 Azo 65000 550, 570Direct Blue 71 Azo 120000 590, 600 Acid Violet 9 Triaryl 46000 540 AcidBlue 80 Anthraquinone 27000 630, 630 Acid Violet 17 Triaryl 53000 520,590 Acid Red 88 Azo 14400 510, 520 Acid Red 150 Azo 23600 520, 530

Example 2

The experiment of example 1 was repeated except the dye level in thewash solution was decreased to 1/10^(th), so that the optical densitywas 0.1 (5 cm path length). Following the washes the Ganz whiteness ofthe cloth was measured (see “assessment of Whiteness and Tint ofFluorescent Substrates with Good Interinstrument Correlation” ColourResearch and Application 19, 1994). The results are displayed in table3, the ganz whiteness values are accurate to +/−5 units. Large increasein the measured Ganz whiteness are found for the substantive blue andviolet dyes with λ_(max) on cotton in the range 570 to 640.

TABLE 3 Dye Ganz whiteness Control 150 Acid Black 1 171 Food Black 1 155Direct Blue 1 190 Direct Violet 51 208 Direct Blue 71 205 Acid Violet 9153 Acid Blue 80 152 Acid Violet 17 170

Acid black 1, direct blue 1, direct violet 51, direct blue 71 and acidviolet 17 gave the greatest increase in Ganz whiteness.

Direct violet 51 and direct blue 71 gave a higher Ganz whiteness valuethan direct blue 1 and they have the further advantage over direct blue1 that they are not metabolised in the body to give carcinogenic amine,unlike the huge number of direct blue and violet dyes (e.g. directblue 1) which contain moieties which breakdown to give the carcinogenicbenzidine, 3,3′dimethoxybenzidine or 3,3′-dimethylbenzidine. These dyesalso have an advantage over many direct violet dyes which containtransition metals that are hazardous to the environment and to humans.

Preferred direct dyes fall into two groups: The first group comprisestris-azo direct blue dyes based on the structure:

where at least two of the A, B and C napthyl rings are substituted by asulphonate group. The C ring may be substituted at the 5 position by anNH₂ or NHPh group, X is a benzyl or napthyl ring substituted with up to2 sulphonate groups and may be substituted at 2 position with a OH groupand may also be substituted with an NH₂ or NHPh group.

Non-limiting examples of these dyes are direct blue 34, 70, 71, 72, 75,78, 82, 120.

The second group comprises bis-azo direct violet dyes based on thestructure

where Z is H or phenyl. The A ring is preferably substituted by a methyland methoxy group at the positions indicated by arrows. The A ring mayalso be a naphthyl ring. The Y group is a benzyl or naphthyl ring, whichis substituted by sulphate group and may be mono or disubstituted bymethyl groups.

Non-limiting examples of these dyes are direct violet 5, 7, 11, 31, 51.The invention also comprises compositions including a single dye of thestructure of the first or second group, or mixtures thereof, the dye ormixture having the defined peak absorption wavelength.

Example 3

The experiment of example 1 was repeated except using dyes at lowerconcentrations, such that the optical density (5 cm) was approximately0.05 and 0.025 giving faintly coloured wash liquors (i.e. using dyelevels 1/20 and 1/40^(th) of experiment 1). Following washing and dryingthe increase in whiteness was measured by a reflectometer and expressedin Ganz units. The Ganz values are accurate to +/−5 units. The resultsare shown in the Table 3 below.

TABLE 4 Ganz whiteness dye OD~0.05 OD~0.025 control 156 156 Direct Blue1 163 175 Direct Violet 51 153 184 Direct Blue 71 171 185

Direct blue 71 gave the best results.

Example 4

Example 3 was repeated but using the blue dye Acid Black 1, the red dyesAcid Red 88 and Acid Red 150, and mixtures thereof. The results areshown in the tables below.

TABLE 5 Ganz whiteness dye OD~0.05 OD~0.025 control 154 154 Acid Black 1160 (A) 160 (B) Acid Red 88 150 (C) 152 (D) Acid Red 150 164 (E) 160 (F)

TABLE 6 Dye Mixture Ganz whiteness control 154 (A) + (C) 173 (A) + (D)175 (A) + 0.5(D) 171 (A) + (E) 176 (A) + (F) 175 (A) + 0.5(F) 169

The results show that mixtures of red and blue dyes gives a greaterincrease in whiteness than either alone. This is because the mixtureproduces a violet shade.

1. A laundry treatment composition which comprises a surfactant and from0.0001 to 0.1 wt % of a combination of dyes which together have a visualeffect on the human eye as a single dye having a peak absorptionwavelength on cotton of from 540 nm to 650 nm, combination comprising aphotostable dye which is substantive to cotton, wherein the photostabledye is a cationic dye and is an azo dye.
 2. A composition as claimed inclaim 1, which is a laundry detergent composition.
 3. A composition asclaimed in claim 2, wherein the detergent composition is a particulatedetergent composition.
 4. A composition as claimed in claim 1, which isa laundry fabric conditioner.
 5. A composition as claimed in claim 1wherein the surfactant is a non-soap surfactant.
 6. A composition asclaimed in claim 5, wherein the surfactant is an anionic or cationicsurfactant.
 7. A composition as claimed in claim 6, wherein thesurfactant is C₈-C₁₅ linear alkyl benzene sulphonate.
 8. A compositionas claimed in claim 1, which comprises from 5 to 60 wt % of surfactant.9. A composition as claimed in claim 1, which comprises fluorescer. 10.A composition as claimed in claim 1, which comprises from 0.0005 to 0.05wt % of dye.
 11. A composition as claimed in claim 1, which comprisesfrom 0.001 to 0.01 wt % of dye.
 12. A composition as claimed in claim 1,wherein the peak absorption wavelength on cotton is from 570 mn to 630mn.